US9048295B2 - Method of manufacturing semiconductor device - Google Patents
Method of manufacturing semiconductor device Download PDFInfo
- Publication number
- US9048295B2 US9048295B2 US14/010,627 US201314010627A US9048295B2 US 9048295 B2 US9048295 B2 US 9048295B2 US 201314010627 A US201314010627 A US 201314010627A US 9048295 B2 US9048295 B2 US 9048295B2
- Authority
- US
- United States
- Prior art keywords
- layer
- substrate
- metal
- electroplated
- electrolessly plated
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 178
- 229910052751 metal Inorganic materials 0.000 claims abstract description 139
- 239000002184 metal Substances 0.000 claims abstract description 139
- 238000009713 electroplating Methods 0.000 claims abstract description 59
- 238000007772 electroless plating Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 238000009792 diffusion process Methods 0.000 claims description 98
- 230000000903 blocking effect Effects 0.000 claims description 88
- 238000007747 plating Methods 0.000 claims description 83
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 36
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 31
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000005324 grain boundary diffusion Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 230000006870 function Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 95
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 78
- 239000010931 gold Substances 0.000 description 49
- 238000010438 heat treatment Methods 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- -1 chlorine ions Chemical class 0.000 description 19
- 230000003213 activating effect Effects 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 8
- 239000010948 rhodium Substances 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000005282 brightening Methods 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 239000006179 pH buffering agent Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- WIEZTXFTOIBIOC-UHFFFAOYSA-L azane;dichloropalladium Chemical compound N.N.Cl[Pd]Cl WIEZTXFTOIBIOC-UHFFFAOYSA-L 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- 150000003476 thallium compounds Chemical class 0.000 description 2
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 2
- 229940119523 thallium sulfate Drugs 0.000 description 2
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 2
- UFVDXEXHBVQKGB-UHFFFAOYSA-L thallous malonate Chemical compound [Tl+].[Tl+].[O-]C(=O)CC([O-])=O UFVDXEXHBVQKGB-UHFFFAOYSA-L 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- DYCJFJRCWPVDHY-UHFFFAOYSA-N 2-(hydroxymethyl)-5-[6-[(4-nitrophenyl)methylsulfanyl]purin-9-yl]oxolane-3,4-diol Chemical compound OC1C(O)C(CO)OC1N1C2=NC=NC(SCC=3C=CC(=CC=3)[N+]([O-])=O)=C2N=C1 DYCJFJRCWPVDHY-UHFFFAOYSA-N 0.000 description 1
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-Threitol Natural products OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 229910021202 NaH2PO2.H2O Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- OBITVHZFHDIQGH-UHFFFAOYSA-N [Au].[K]C#N Chemical compound [Au].[K]C#N OBITVHZFHDIQGH-UHFFFAOYSA-N 0.000 description 1
- OJIGKQJSYOZYDD-UHFFFAOYSA-N [C-]#N.[K+].[Au+2].[C-]#N.[C-]#N Chemical compound [C-]#N.[K+].[Au+2].[C-]#N.[C-]#N OJIGKQJSYOZYDD-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- KTMKVAKYQAXRSR-UHFFFAOYSA-K azanium;pyridine-2,6-dicarboxylate;rhodium(3+) Chemical compound [NH4+].[Rh+3].[O-]C(=O)C1=CC=CC(C([O-])=O)=N1.[O-]C(=O)C1=CC=CC(C([O-])=O)=N1 KTMKVAKYQAXRSR-UHFFFAOYSA-K 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
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- 229960000956 coumarin Drugs 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- SRRYZMQPLOIHRP-UHFFFAOYSA-L dipotassium;tellurate Chemical compound [K+].[K+].[O-][Te]([O-])(=O)=O SRRYZMQPLOIHRP-UHFFFAOYSA-L 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
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- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- UESISTHQAYQMRA-UHFFFAOYSA-M formyloxythallium Chemical compound [Tl+].[O-]C=O UESISTHQAYQMRA-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- MDECNDDIBYOQGF-UHFFFAOYSA-L gold(1+);sulfite Chemical group [Au+].[Au+].[O-]S([O-])=O MDECNDDIBYOQGF-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- ZPBSAMLXSQCSOX-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 ZPBSAMLXSQCSOX-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229940097322 potassium arsenite Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- HEQWEGCSZXMIJQ-UHFFFAOYSA-M potassium;oxoarsinite Chemical compound [K+].[O-][As]=O HEQWEGCSZXMIJQ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229940000207 selenious acid Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- YZFKUFJKKKTKSB-UHFFFAOYSA-J trisodium;gold(1+);disulfite Chemical compound [Na+].[Na+].[Na+].[Au+].[O-]S([O-])=O.[O-]S([O-])=O YZFKUFJKKKTKSB-UHFFFAOYSA-J 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
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- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4871—Bases, plates or heatsinks
- H01L21/4875—Connection or disconnection of other leads to or from bases or plates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a method of manufacturing a semiconductor device wherein a metal functioning as a radiator or an electrode is formed on a substrate, and also relates to semiconductor devices manufactured by this manufacturing method.
- a Cu diffusion blocking layer is formed between a substrate and an overlying Cu layer by a vacuum film-forming method such as vacuum deposition.
- the vacuum film-forming method can be used to form films of various metals.
- a Cu diffusion blocking layer may be formed of Ta by a vacuum film-forming method so as to achieve enhanced Cu diffusion blocking effect.
- Japanese Laid-Open Patent Publication No. 2011-165810 discloses a technique for forming a Pd plating layer on a GaAs substrate by means of electroless plating. This publication also discloses that a metal layer of Cu, etc. may be formed on the Pd plating layer.
- a Cu diffusion blocking layer formed by a vacuum film-forming method as disclosed by Chun-Wei CHANG et al. above tends to exhibit inadequate covering ability (or coverage ratio), since vacuum film-forming techniques are anisotropic. It has been found, particularly, that vacuum film-forming methods cannot form a film having high covering ability on substrates having a projection or recess. If a Cu diffusion blocking layer formed on a substrate has low covering ability, a portion of the Cu layer overlying the Cu diffusion blocking layer will be in direct contact with the substrate, so that Cu in the Cu layer diffuses through that portion into the substrate.
- the present invention has been made to solve the above problems. It is, therefore, an object of the present invention to provide a method of manufacturing a semiconductor device in which a layer formed between a substrate and a metal layer has high covering ability and serves to reduce diffusion of components of the metal layer, such as Cu, into the substrate. Another object of the invention is to provide such a semiconductor device.
- a method of manufacturing a semiconductor device includes the steps of immersing a substrate in a solution containing metal ions to adhere a metal catalyst to a surface of the substrate, immersing the substrate with the metal catalyst adhered thereto in an electroless plating solution to electrolessly plate a layer on the substrate, immersing the substrate in an electroplating solution to electroplate a layer on the electrolessly plated layer using the electrolessly plated layer as a power feeding layer, and forming a metal layer of Cu or Ag on the electroplated layer.
- the electroplated layer is formed of a different material than the metal layer.
- a semiconductor device includes a substrate, a first metal layer formed on the substrate, a second metal layer formed on the first metal layer, and a metal layer of Cu or Ag formed on the second metal layer.
- the second metal layer has a larger crystal grain size than the first metal layer.
- a method of manufacturing a semiconductor device includes the steps of immersing a substrate in a solution containing metal ions to adhere a metal catalyst to a surface of the substrate, immersing the substrate with the metal catalyst adhered thereto in an electroless plating solution to electrolessly plate a layer on the substrate, plating an Au layer on the electrolessly plated layer, immersing the substrate in an electroplating solution to electroplate a layer on the plated Au layer using the electrolessly plated layer and the plated Au layer as power feeding layers, and forming a metal layer of Cu or Ag on the electroplated layer.
- the electroplated layer is formed of a different material than the metal layer.
- FIG. 1 is a cross-sectional view of a semiconductor device in accordance with a first embodiment of the present invention
- FIGS. 2A and 2B are cross-sectional views illustrating the difference in covering ability by layers formed by vapor deposition and plating, respectively;
- FIGS. 3A and 3B are graphs illustrating fine crystallization of an electrolessly plated layers in response to heating
- FIG. 4 is a graph showing alloying of an electrolessly plated layer of Pd
- FIG. 5 is a cross-sectional view of a semiconductor device having a substrate with a recess formed therein;
- FIG. 6 is a cross-sectional view of a semiconductor device having a substrate with a recess formed therein;
- FIG. 7 is a cross-sectional view of a semiconductor device having a substrate with a projection formed thereon;
- FIG. 8 is a cross-sectional view of a semiconductor device having a substrate with a projection formed thereon;
- FIG. 9 is a cross-sectional view of a semiconductor device having a substrate with a through-hole formed therein;
- FIG. 10 is a cross-sectional view of the semiconductor device of the second embodiment
- FIG. 11 is a graph comparing the Cu diffusion blocking effect of three different samples.
- FIG. 12 is a cross-sectional view of the semiconductor device of the third embodiment.
- FIG. 13 is a cross-sectional view of a substrate
- FIG. 14 is a cross-sectional view of the substrate after the support substrate has been bonded thereto;
- FIG. 15 is a cross-sectional view of the substrate after the via hole has been formed therein;
- FIG. 16 is a cross-sectional view of the substrate after the heat-radiating electrode has been formed thereon;
- FIG. 17 is an enlarged view of the portion shown in the dashed line of FIG. 16 ;
- FIG. 18 is a cross-sectional view of the semiconductor device of the fifth embodiment.
- FIG. 19 shows the amount of change in sheet resistance.
- FIG. 1 is a cross-sectional view of a semiconductor device in accordance with a first embodiment of the present invention.
- This semiconductor device includes a substrate 10 formed of GaAs.
- a Pd—Ga—As layer 12 is formed on the substrate 10 .
- a first metal layer is formed on the substrate 10 , with the Pd—Ga—As layer 12 interposed therebetween.
- the first metal layer is formed of NiP material by electroless plating and hence referred to herein as the electrolessly plated layer 14 .
- a second metal layer is formed on the first metal layer (or electrolessly plated layer 14 ).
- the second metal layer is formed by electroplating and hence referred to herein as the electroplated layer 16 .
- the electroplated layer 16 is formed of Pd.
- it may be formed of Ru, Pt, or Rh instead of Pd.
- the second metal layer (or electroplated layer 16 ) has a larger crystal grain size than the first metal layer (or electrolessly plated layer 14 ).
- the electrolessly plated layer 14 and the electroplated layer 16 may be hereinafter referred to collectively as the diffusion blocking layer 17 .
- an Au layer may be plated on the first metal layer, and the second metal layer may be formed on this plated Au layer.
- the plated Au layer is interposed between the first metal layer and the second metal layer. This prevents cracking of the second metal layer, and furthermore the second metal layer is adhered to the first metal layer by the plated Au layer.
- the plated Au layer may be produced using any type of plating solution including, but not limited to, a displacement Au plating solution. Further, the plated Au layer may have a thickness of, e.g., approximately 50 nm, or less.
- a metal layer 18 of Cu is formed on the second metal layer (or electroplated layer 16 ).
- the metal layer 18 has a thickness of, e.g., approximately 1-5 ⁇ m.
- the Pd—Ga—As layer 12 , the electrolessly plated layer 14 , the electroplated layer 16 , and the metal layer 18 serve to enhance the heat dissipation from the semiconductor device and to provide electrical contact.
- the metal layer 18 is preferably formed to have a greater thickness than the other layers (i.e., the Pd—Ga—As layer 12 , the electrolessly plated layer 14 , and the electroplated layer 16 ), since the metal layer 18 is formed of Cu and hence has relatively good heat dissipation characteristics and low electrical resistivity.
- a substrate 10 is immersed in a solution containing metal ions so as to adhere a metal catalyst to the surface of the substrate 10 .
- the metal ion-containing solution is a Pd activating solution containing Pd ions, such as a palladium chloride solution.
- the Pd activating solution has a Pd concentration of, e.g., approximately 0.1-1.0 g/L.
- the substrate 10 is immersed in the Pd activating solution at 20-30° C. for approximately 1-5 minutes while the Pd activating solution is stirred so that a metal catalyst adheres to the surface of the substrate 10 .
- the metal catalyst i.e., Pd catalyst
- the Pd—Ga—As layer 12 thus formed contains a metal catalyst 12 a.
- the Pd concentration and temperature of the Pd activating solution affects the amount and uniformity of Pd catalyst that adheres to the substrate 10 , it is necessary to adjust these parameters of the Pd activating solution so that the interface between the substrate 10 and the Pd—Ga—As layer 12 has adequate adhesion, thereby preventing delamination of the Pd—Ga—As layer 12 , and so that the Pd—Ga—As layer 12 has appropriate surface morphology.
- the electroless plating solution may be, e.g., a nickel sulfate solution containing sodium hypophosphite as a reducing agent and an organic acid as a complexing agent.
- This solution has a Ni concentration of approximately 1-1.5 g/L.
- the P concentration of the solution may be adjusted so that the electrolessly plated layer 14 has a P content of approximately 8-10%.
- Such an electrolessly plated Ni layer has higher corrosion resistance than a pure Ni layer.
- the electroless plating solution is set at a temperature of 60-80° C. and stirred during the immersion of the substrate 10 in the electroless plating solution.
- the substrate 10 is immersed in an electroplating solution, and a layer 16 of Pd is electroplated on the electrolessly plated layer 14 using the electrolessly plated layer 14 as a power feeding layer (i.e., by supplying electricity through the electrolessly plated layer 14 ).
- the substrate 10 is immersed in an electroplating solution, and a DC power supply is connected to the substrate 10 and a separate platinum-coated titanium electrode (which is also immersed in the electroplating solution) so that the electrolessly plated layer 14 acts as a cathode and the titanium electrode acts as an anode.
- the electroplating solution is, e.g., a solution containing a palladium salt, such as diamminedichloropalladium(II) [PdCl 2 (NH 3 ) 2 ], and a conductive salt, such as NH 4 Cl.
- the Pd concentration of the solution is, e.g., approximately 0.1-0.5%.
- the electroplating solution is set at a temperature of 40-60° C. during the immersion of the substrate 10 in the electroplating solution. It should be noted that the electroplated layer 16 is formed of Pd and a metal layer 18 that is subsequently formed on the electroplated layer 16 is formed of Cu; that is, they are made of different materials.
- the metal layer 18 of Cu is formed on the electroplated layer 16 .
- the substrate 10 is immersed in a Cu plating solution, and a DC power supply is connected to the substrate 10 and a separate phosphor copper electrode (which is also immersed in the Cu plating solution) so that the electroplated layer 16 acts as a cathode and the phosphor copper electrode acts as an anode.
- a current is then applied between the cathode (the electroplated layer 16 ) and the anode (the phosphor copper electrode) to effect electroplating of the electroplated layer 16 with Cu.
- the Cu plating solution is, e.g., a solution containing copper sulfate, sulfuric acid, chlorine ions, and/or organic additive agents. When chlorine ions are used, hydrochloric acid may be added to the plating bath to adjust the chlorine ion concentration.
- the semiconductor device of the first embodiment includes the diffusion blocking layer 17 formed between the substrate 10 and the metal layer 18 .
- the diffusion blocking layer 17 is required to have “high covering ability” so as to be able to completely fill the interface between the metal layer 18 and the substrate 10 and is also required to be “of such a film quality as to have a significant diffusion blocking effect.”
- the following describes the high covering ability of the diffusion blocking layer 17 of the first embodiment.
- FIGS. 2A and 2B are cross-sectional views illustrating the difference in covering ability by layers formed by vapor deposition and plating, respectively.
- FIG. 2A is a cross-sectional view of a layer 32 formed by vapor deposition on a substrate 30 having an opening 30 A.
- FIG. 2B is a cross-sectional view of a layer 34 formed by plating on the same substrate 30 having the opening 30 A.
- a comparison of FIGS. 2A and 2B indicates that the layer 34 formed by plating has higher covering ability than the layer 32 formed by vapor deposition. More specifically, the deposited layer 32 fails to fully cover the side wall of the opening 30 A, whereas the plated layer 34 completely covers the walls of the opening 30 A (i.e., exhibits high covering ability).
- plating is a film-forming method capable of forming a film having high covering ability, as compared with other film-forming methods such as vapor deposition, sputtering, CVD, and ion plating. Since the diffusion blocking layer 17 of the first embodiment is made up of the electrolessly plated layer 14 and the electroplated layer 16 , which are produced by plating, the diffusion blocking layer 17 has high covering ability. Therefore, the diffusion blocking layer 17 can be formed to completely fill the interface between the metal layer 18 and the substrate 10 .
- the diffusion blocking layer 17 is of such a film quality as to have a significant diffusion blocking effect. Copper (Cu) in the metal layer 18 migrates to the diffusion blocking layer 17 and diffuses therein primarily via grain boundary diffusion. Therefore, the diffusion blocking layer 17 is preferably amorphous, which means that it has no grain boundaries.
- the electrolessly plated layer 14 of the diffusion blocking layer 17 is amorphous, hence has no grain boundaries, and is capable of preventing grain boundary diffusion immediately after its formation, the electrolessly plated layer 14 transforms into a fine crystalline form when later subjected to heat treatment, e.g., at approximately 200° C.
- FIGS. 3A and 3B are graphs illustrating fine crystallization of an electrolessly plated layer in response to heating.
- FIG. 3A shows x-ray diffraction results of a sample before it was subjected to heat treatment. This sample was produced by electrolessly plating a layer of Pd on a GaAs substrate to a thickness of 300 nm and then further electrolessly plating a layer of NiP on the electrolessly plated Pd layer to a thickness of 100 nm.
- the diffraction peak shown in FIG. 3A is broad, indicating that the sample (made up of two electrolessly plated layers, as described above) was amorphous immediately after its formation.
- FIG. 3B shows x-ray diffraction results of the sample after it was subjected to heat treatment at 250° C. for 4 hours.
- the x-ray diffraction results of FIG. 3B exhibit a plurality of peaks, indicating crystallization of the sample (made up of two electrolessly plated layers). It follows from these x-ray diffraction results of the sample that the electrolessly plated layer 14 of the present embodiment transforms into an aggregate of small-sized crystal grains when subjected to heat treatment and hence has many grain boundaries after the heat treatment, resulting in a decreased Cu diffusion blocking effect.
- the electroplated layer 16 which is produced by electroplating, has a larger crystal grain size than the electrolessly plated layer 14 . Therefore, the electroplated layer 16 has fewer grain boundaries and hence a higher Cu diffusion blocking effect than the electrolessly plated layer 14 . Further, it is possible to minimize the diffusion of atoms from the electroplated layer 16 into adjacent layers when the electroplated layer 16 is heat treated, since the electroplated layer 16 has relatively few grain boundaries. Thus, the electroplated layer 16 has high thermal stability, resulting in an enhanced Cu diffusion blocking effect of the diffusion blocking layer 17 . In other words, the diffusion blocking layer 17 is of such a film quality as to have a significant diffusion blocking effect, since it includes the electroplated layer 16 .
- the Cu diffusion blocking effect of the electrolessly plated layer 14 is relatively small, since it includes many grain boundaries.
- the electrolessly plated layer 14 serves as a power feeding layer when forming the electroplated layer 16 . That is, since the substrate 10 has low conductivity, it is not possible to directly electroplate a layer on the substrate 10 . Therefore, the electrolessly plated layer 14 is provided on the substrate 10 and used as a power feeding layer for forming the electroplated layer 16 . Further, the electrolessly plated layer 14 also serves as an adhesion layer for enhancing the adhesion between the substrate 10 and the metal layer 18 .
- FIG. 4 is a graph showing alloying of an electrolessly plated layer of Pd.
- This sample (or electrolessly plated layer) was produced by electrolessly plating a layer of Pd on a GaAs substrate to a thickness of 100 nm and then heat-treating the layer in a nitrogen atmosphere at 250° C. for 4 hours. An elemental depth profile of this sample was obtained using depth Auger electron spectroscopy.
- the electrolessly plated layer 14 is preferably formed of NiP if the substrate 10 is GaAs.
- FIG. 5 is a cross-sectional view of a semiconductor device having a substrate 30 with a recess 30 B formed therein.
- FIG. 6 is a cross-sectional view of a semiconductor device having a substrate 30 with a recess 30 C formed therein.
- FIG. 7 is a cross-sectional view of a semiconductor device having a substrate 30 with a projection 30 D formed thereon.
- FIG. 8 is a cross-sectional view of a semiconductor device having a substrate 30 with a projection 30 E formed thereon.
- FIG. 9 is a cross-sectional view of a semiconductor device having a substrate 30 with a through-hole 30 F formed therein.
- a recess, projection, or through-hole When a recess, projection, or through-hole is to be formed in the surface of a substrate, it is produced by dry etching, such as reactive ion etching or plasma etching, or by wet etching in acid or alkali.
- dry etching such as reactive ion etching or plasma etching
- wet etching is particularly likely to cause side etching, or undercut.
- certain wet etching solutions exhibit a difference in etching rate between different crystal plane orientations and between different crystal materials of the object to be etched, thereby etching the object into a mesa or inverted mesa shape.
- the diffusion blocking layer 17 is formed by plating and hence exhibits high covering ability even if the surface of the substrate is provided with a recess, projection, or through-hole.
- the metal layer 18 is formed of Cu and hence is low-cost, as compared to layers formed of noble metals such as Au.
- the metal layer 18 may be formed of Ag instead of Cu. Since Ag has higher electrical and thermal conductivity than any other metal, if the metal layer 18 is formed of Ag, the semiconductor device can be manufactured to have high electrical conductivity and good heat dissipation characteristics. It should be noted that the metal layer 18 may be formed using any suitable method such as vapor deposition, sputtering, or plating, whether it is formed of Cu or Ag.
- Cu when a layer of Cu (such as the metal layer 18 ) is formed on a substrate having a recess, Cu may be grown or deposited selectively in the recess relative to flat portions of the substrate so as to fill the recess. This is preferably achieved by an electroplating method.
- the plating solution used is a copper sulfate plating bath containing, e.g., sulfuric acid, chlorine ions, and organic additive agents. These additive agents include an accelerating agent (an accelerator or brightener), a suppressing agent (a suppressor or carrier), or a leveling agent (or leveler).
- the substrate 10 may be subjected to pretreatment such as oxygen ashing or ozone ashing before a metal catalyst is adhered to the surface of the substrate 10 .
- pretreatment such as oxygen ashing or ozone ashing
- the substrate 10 may be cleaned in an acid or alkali solution having the effect of removing surface oxide films.
- hydrofluoric acid-based solution treatment is preferably used to remove surface oxide films from Si and SiC substrates
- hydrochloric acid-based solution treatment is preferably applied to remove surface oxide films from GaAs and GaN substrates.
- sulfuric acid-based or hydrofluoric acid-based solution treatment is preferably applied to InP substrates.
- the electrolessly plated layer 14 may be formed of an elemental metal, such as Ni, Co, Pd, Cu, Ag, Au, Pt, Sn, Ru, or Rh, or an alloy, such as NiB, NiCoWP, NiMoP, CoP, CoNiP, CoWP, CoSnP, CoZnP, or CoMnP. Alloy plating has different properties than elemental metal plating; for example, alloy plating provides enhanced corrosion resistance.
- elemental metal such as Ni, Co, Pd, Cu, Ag, Au, Pt, Sn, Ru, or Rh
- an alloy such as NiB, NiCoWP, NiMoP, CoP, CoNiP, CoWP, CoSnP, CoZnP, or CoMnP. Alloy plating has different properties than elemental metal plating; for example, alloy plating provides enhanced corrosion resistance.
- Electroless plating solutions comprise a metal salt, a reducing agent, a buffering agent, a complexing agent, and a fixing agent, etc.
- metal salts include nickel sulfate, nickel chloride, nickel acetate, nickel carbonate, nickel sulfamate, and other nickel salts
- reducing agents include sodium phosphinate (NaH 2 PO 2 .H 2 O) and dimethylamine borane (DMAB)
- examples of buffering agents include monocarboxylic acids (such as formic acid and acetic acid) and alkali metal salts thereof
- complexing agents includes organic acids (such as citric acid), ethylenediamine tetraacetic acid (EDTA), and ammonia, etc.
- Electroless Pd plating solutions are often prepared using a palladium chloride (a palladium salt).
- the reducing agent used is typically ethylenediamine tetraacetic acid (EDTA) used together with a phosphinate serving as a complexing agent.
- EDTA ethylenediamine tetraacetic acid
- Electroless Au plating solutions are broadly divided into two types: displacement Au plating solutions, which are used for displacement plating of a substrate metal surface with Au; and autocatalytic Au plating solutions, which contain a reducing agent for depositing a gold film.
- Displacement Au plating solutions are prepared using sodium gold sulfite with the addition of complexing agents such as a sulfite salt, mercaptosuccinic acid, and ethylenediamine tetraacetic acid (EDTA).
- a chelating agent may be added to the solutions to fix metal ions during plating.
- any suitable type of water-soluble chelating agent may be used; typical examples of such chelating agents include thallium compounds such as thallium sulfate, thallium nitrate, thallium oxide, thallium chloride, and thallium malonate.
- Autocatalytic Au plating solutions are used in a strongly alkaline bath and prepared using a gold cyanide complex, such as gold(I) potassium cyanide (KAu(CN) 2 ) or gold(II) potassium cyanide (KAu(CN) 4 ), with the addition of potassium tetrahydroborate or dimethylamine borane (DMAB) as a reducing agent.
- a gold cyanide complex such as gold(I) potassium cyanide (KAu(CN) 2 ) or gold(II) potassium cyanide (KAu(CN) 4 )
- DMAB dimethylamine borane
- electroless Cu plating solutions are prepared using copper sulfate as a metal salt for supplying copper ions, with the addition of a reducing agent.
- a typical example of a reducing agent is formaldehyde.
- Other examples of reducing agents include potassium tetrahydroborate, dimethylamine borane, and glyoxylic acid.
- the plating bath is made strongly alkaline.
- Examples of PH control agents include sodium hydroxide, potassium hydroxide, and lithium hydroxide.
- copper ions tend to be precipitated as hydroxide.
- complexing agents for preventing such precipitation include Rochelle salt, EDTA, glycerol, meso-erythritol, adonitol, D-mannitol, D-sorbitol, dulcitol, iminodiacetic acid, trans-1,2-cyclohexanediamine tetraacetic acid, triethanolamine, and ethylenediamine.
- a decrease in the stability of the bath e.g., decomposition of the plating solution, is caused primarily by copper powder in the solution, which powder is generated by disproportionation reaction of CuO 2 (CuO2+H2O ⁇ Cu+Cu2++20H—).
- Methods for avoiding this problem include agitation of the plating solution by air and addition of a fixing agent to the bath.
- fixing agents include cyanide, thiourea, bipyridyl, o-phenanthroline, and neocuproine, which form a complex preferentially with monovalent copper.
- An accelerating agent such as 8-hydroxy-7-iodo-5-quinolinesulfonic acid is added to the plating bath to increase the plating rate without degrading the stability of the bath.
- Electroless Pt plating solutions are prepared using a platinum salt, such as dinitrodiammine platinum or potassium tetranitro-platinate, a reducing agent, such as hydrazine, and a fixing agent, such as hydroxylamine salt.
- a platinum salt such as dinitrodiammine platinum or potassium tetranitro-platinate
- a reducing agent such as hydrazine
- a fixing agent such as hydroxylamine salt.
- Electroless Rh plating solutions are prepared using a rhodium salt, such as rhodium amine nitrite, rhodium chloride amine, ammonium di(pyridine-2,6-dicarboxylate) rhodium(III), rhodium acetate, or rhodium chloride, and a reducing agent, such as hydrazine or sodium tetrahydroborate.
- a rhodium salt such as rhodium amine nitrite, rhodium chloride amine, ammonium di(pyridine-2,6-dicarboxylate) rhodium(III), rhodium acetate, or rhodium chloride
- a reducing agent such as hydrazine or sodium tetrahydroborate.
- Electroless Ru plating solutions are prepared using a ruthenium salt, such as tetraamminediaquaruthenium phosphate or ruthenium sulfate, and a reducing agent, such as sodium tetrahydroborate.
- the plating solutions are used in a plating bath which is made alkaline by addition of ammonia, etc., or made acidic by addition of sulfuric acid, etc.
- Electroless Co plating solutions are prepared using cobalt sulfate and sodium phosphinate as its principal components, with the addition of a complexing agent such as a citrate, tartrate, or pyrophosphate.
- a complexing agent such as a citrate, tartrate, or pyrophosphate.
- metals which can be electroplated include Zn, Ir, In, Cd, Au, Ag, Cr, Co, Sn, Fe, Cu, Pb, Ni, Pt, Pd, Bi, Mn, Mo, Rh, and Ru. Any suitable method can be used to produce the electroplated layer 16 . Examples of such methods include DC plating, pulse plating, and reverse pulse plating. Electroplating solutions comprise a metal salt, an electrically conductive salt, an anode dissolution accelerating agent, a complexing agent, and additive agents, etc. It should be noted that when the substrate to be plated has a via structure, pulse plating or reverse pulse plating may be used to enhance the covering ability of the electroplated layer, as compared to the use of DC plating.
- Nickel (Ni) electroplating solutions are used in an acidic bath such as a Watt bath, a chloride bath, a sulfamate bath, or a Wood's bath.
- the Watt bath contains nickel sulfate, nickel chloride, and boric acid, etc.
- the chloride bath contains nickel chloride and boric acid, etc.
- the sulfamate bath contains nickel sulfamate, nickel chloride, and boric acid, etc.
- the Wood's bath contains nickel chloride and hydrochloric acid, etc.
- Nickel electroplating solutions may contain an anode solubilzing agent, a PH buffering agent, or additive agents for reducing stress in electrodeposits or improving surface conditions.
- additive agents include primary brightening agents, such as saccharine, naphthalene sodium (di-, tri-) sulfonate, sulfonamide, and sulfinic acid, and secondary brightening agents, such as 1,4-butynediol and coumarin.
- Anodes used for nickel plating preferably have a high degree of purity and uniformly dissolve during plating without generation of anode slime.
- anode materials include electrolytic nickel, depolarized nickel, carbonized nickel, and sulfur-containing nickel.
- Pd electroplating solutions are prepared using diamminedichloropalladium(II) [PdCl 2 (NH 3 ) 2 ] (a palladium salt), a conductive salt, and a pH buffering agent (NH 4 Cl or K 2 HPO 4 ). They are used in a neutral or alkaline ammine complex bath.
- the anode used is an insoluble anode such as a platinum-coated titanium electrode.
- the bath may contain an organic compound, such as saccharine or 1,3,6-naphthalene trisulfonate, as a primary brightening agent, and may also contain another organic compound, such as coumarin, as a secondary brightening agent.
- Ruthenium (Ru) electroplating solutions are prepared using ruthenium sulfate (a ruthenium salt) and used in a plating bath which is made acidic by addition of sulfamic acid, etc.
- Pt electroplating solutions are prepared using cis-dinitrodiamine platinum (a platinum salt), and used in a plating bath which is made neutral or acidic by addition of ammonium nitrite, sodium nitrite, or aqueous ammonia, etc.
- Gold (Au) electroplating solutions are typically prepared so as to form a cyanide bath or a sulfurous acid bath.
- alkaline cyanide baths contain a gold salt, potassium gold(I) cyanide, potassium cyanide serving as a free-cyanide-ion source, potassium carbonate for enhancing electrodeposition, and dipotassium hydrogenphosphate serving as a pH buffering agent.
- sulfurous acid baths contain a gold salt, sodium gold(I) sulfite, sodium sulfite, and phosphorous acid and are adjusted to approximately pH8.
- these baths may contain a trace amount of a thallium compound and/or a trace amount of ethylene diamine, etc. serving as a fixing agent for reducing decomposition of gold(I) sulfite complex.
- the additive concentration may be managed using a Hull cell test or cyclic voltammetric stripping (CVS), etc.
- Copper sulfate electroplating bath When the metal layer 18 is to be formed of Cu, a copper sulfate electroplating bath, a copper pyrophosphate electroplating bath, or a copper cyanide electroplating bath may be used. Copper sulfate baths are often used for the manufacture of semiconductor devices. Copper sulfate baths typically comprise CuSO 4 .5H 2 O, sulfuric acid, chlorine ions, and organic additive agents. These additive agents often include an accelerating agent (an accelerator or brightener), a suppressing agent (a suppressor or carrier), and/or a leveling agent (or leveler), especially when a via structure is to be filled with Cu.
- an accelerator or brightener an accelerator or brightener
- suppressing agent a suppressor or carrier
- leveling agent or leveler
- the accelerating agent has the effect of promoting the growth, or deposition, of copper preferentially on the bottoms of the vias, and the suppressing agent adheres to the plated copper surface so as to suppress the growth of copper outside the vias.
- the leveling agent acts on the suppressing agent so that the suppressing agent moves in the solution at a speed equal to the diffusion limitation, thereby suppressing the growth of copper outside the vias. Since these agents serve their functions with the aid of chlorine ions, it is important to control the concentration of chlorine ions, as well as those of the additive agents.
- suppressing agents include polyether compounds, typified by polyethylene glycol (PEG).
- accelerating agents include organic sulfur compounds having a sulfo group, typified by bis(3-sulfopropyl)disulfide (SPS).
- leveling agents include quatemary amine compounds, typified by Janus Green B (JGB).
- the electroplating bath for forming the metal layer 18 is preferably maintained at approximately 20-30° C.
- the anode used is typically a soluble anode and is preferably made of high phosphorous copper in order to minimize generation of anode slime.
- the anode preferably has a phosphorous content of approximately 0.04-0.06%.
- the material of the substrate 10 is not limited to GaAs.
- the substrate 10 may be formed of Si, SiC, GaN, or InP instead of GaAs.
- at least one epitaxial layer may be formed on the substrate 10 , and the diffusion blocking layer 17 may be formed on the at least one epitaxial layer.
- the substrate 10 When the substrate 10 is formed of a compound semiconductor such as GaAs, the substrate 10 is highly reactive with the metal activating solution used, which facilitates adhesion between the substrate and the electrolessly plated layer formed thereon.
- the substrate 10 When the substrate 10 is formed of Si-based material, on the other hand, it is difficult to ensure adhesion between the substrate 10 and the electrolessly plated layer 14 , since the substrate 10 is poorly reactive with the metal activating solution.
- the substrate may be subjected to catalyst treatment using a metal activating solution containing buffered hydrofluoric acid after forming a silicon oxide film on the surface of the substrate (see Japanese Laid-Open Patent Publication No. 2005-336600).
- the solution baths for storing the metal activating solution (Pd activating solution), the electroless plating solution, or the electroplating solution may be made of a material such as borosilicate glass which is resistant to high temperatures and to the formation of a film thereon, in order to minimize the formation of a film on the solution baths.
- the cassette is preferably formed of a material having chemical resistance, such as a perfluoroalkoxy fluoroplastic (PFA).
- PFA perfluoroalkoxy fluoroplastic
- the stirring bar used in the plating process and the handle used for holding the cassette may also be formed of a material having chemical resistance.
- a second embodiment of the present invention provides a method of manufacturing a semiconductor device and also provides a semiconductor device. These method and semiconductor device have many features common to the method and semiconductor device of the first embodiment. Therefore, the following description of the second embodiment will be primarily limited to the differences from the first embodiment.
- FIG. 10 is a cross-sectional view of the semiconductor device of the second embodiment.
- the semiconductor device includes an electroplated layer 50 which contains Ge.
- the electroplated layer 50 is formed in an electroplating solution containing Ge oxide.
- the Ge oxide concentration of the electroplating solution is preferably 0.1-1000 mg/L in terms of Ge atom.
- the use of a Ge oxide-containing electroplating solution to produce the electroplated layer 50 results in co-deposition of the base metal (Pd) and Ge.
- the Ge concentration of the electroplated layer 50 is preferably in the range of from 1 ppm to 10000 ppm, inclusive.
- FIG. 11 is a graph comparing the Cu diffusion blocking effect of three different samples.
- Sample 1 was produced as follows: a first NiP layer (having a thickness of 0.5 ⁇ m) was formed on a GaAs substrate in an electroless plating solution after applying catalyst treatment to the surface of the substrate using a Pd activating solution; a first Pd layer (0.2 ⁇ m) was then formed on the first NiP layer in an electroless plating solution; a Cu layer (a metal layer having a thickness of 3 ⁇ m) was then formed on the first Pd layer in an electroplating solution; a second NiP layer (0.5 ⁇ m) was then formed on the Cu layer in an electroless plating solution; a second Pd layer (0.2 ⁇ m) was then formed on the second NiP layer in an electroless plating solution; and an Au layer (0.05 ⁇ m) was then formed on the second Pd layer in a displacement plating solution.
- the diffusion blocking layer of Sample 1 (between
- Sample 2 was produced as follows: a first NiP layer (0.5 ⁇ m) was formed on a GaAs substrate in an electroless plating solution after applying catalyst treatment to the surface of the substrate using a Pd activating solution; a first Pd layer (0.2 ⁇ m) was then formed on the first NiP layer in an electroplating solution; a Cu layer (a metal layer having a thickness of 3 ⁇ m) was then formed on the first Pd layer in an electroplating solution; a second NiP layer (0.5 ⁇ m) was then formed on the Cu layer in an electroless plating solution; a second Pd layer (0.2 ⁇ m) was then formed on the second NiP layer in an electroplating solution; and an Au layer was then formed on the second Pd layer in a displacement plating solution.
- the diffusion blocking layer of Sample 2 (between the GaAs substrate and the Cu layer) includes an electrolessly plated layer and an electroplated layer.
- Sample 3 was produced as follows: a first NiP layer (0.5 ⁇ m) was formed on a GaAs substrate in an electroless plating solution after applying catalyst treatment to the surface of the substrate using a Pd activating solution; a first Pd layer (0.2 ⁇ m) was then formed on the first NiP layer in an electroplating solution containing Ge oxide; a Cu layer (a metal layer having a thickness of 3 ⁇ m) was then formed on the first Pd layer in an electroplating solution; a second NiP layer (0.5 ⁇ m) was then formed on the Cu layer in an electroless plating solution; a second Pd layer (0.2 ⁇ m) was then formed on the second NiP layer in an electroplating solution; and an Au layer was then formed on the second Pd layer in a displacement plating solution.
- the diffusion blocking layer of Sample 3 (between the GaAs substrate and the Cu layer) includes an electroplated layer containing Ge.
- Samples 1 to 3 have a multilayer structure including GaAs/NiP/Pd/Cu/NiP/Pd/Au layers (where the layer or layers on the right side of each symbol “I” overlie the layer or layers on the left side of the symbol).
- the NiP layer and the Pd layer that are disposed between the GaAs substrate and the Cu layer are electrolessly plated layers.
- the NiP layer and the Pd layer that are disposed between the GaAs substrate and the Cu layer are an electrolessly plated layer and an electroplated layer, respectively.
- Sample 3 is similar in composition to Sample 2, except that the Pd layer between the substrate and the Cu layer contains Ge.
- the vertical axis represents the amount of increase or change in sheet resistance of each sample due to heat treatment, expressed in percentage of the sheet resistance of the sample before the heat treatment, that is, [(the sheet resistance of each sample after heat treatment/that of the sample before the heat treatment) ⁇ 1] ⁇ 100(%); and the horizontal axis represents heat treatment time.
- the amount of change in sheet resistance of each sample due to heat treatment is dependent primarily on the amount of change in resistance of the metal layer of the sample due to the heat treatment, since the metal layer has a relatively large thickness of 3 ⁇ m and relatively low resistivity.
- electroplated layers have a greater Cu diffusion blocking effect than electrolessly plated layers, and the addition of Ge to an electroplated layer further increases its Cu diffusion blocking effect.
- the reason that the electroplated layer 50 containing Ge has an increased Cu diffusion blocking effect is thought to be that Ge in the electroplated layer 50 transforms the grain boundaries of the electroplated layer 50 so as to reduce grain boundary diffusion.
- Ge in the electroplated layer 50 may act to reduce the difference in orientation between adjacent crystal grains and thereby reduce the widths of grain boundaries, or may be located at grain boundaries so as to reduce grain boundary diffusion.
- the electroplated layer 50 contains Ge, it has increased resistance to high temperatures.
- the method of manufacturing a semiconductor device in accordance with the second embodiment uses an electroplating solution containing Ge oxide.
- an electroplating solution containing any suitable compound may be used instead while still retaining the advantages described above.
- Examples of such compounds include Ge compounds, As compounds, Se compounds, B compounds, P compounds, Te compounds, Sb compounds, Tl compounds, Pb compounds, and S compounds which are capable of serving as a crystal control agent for altering the grain boundaries of the electroplated layer.
- Ge compounds include Ge oxide, as described above.
- Examples of such As compounds include potassium arsenite.
- Se compounds include selenious acid.
- B compounds include dimethylamine borane.
- Examples of such P compounds include sodium hypophosphite.
- Examples of such Te compounds include potassium tellurate.
- the electroplated layer 50 can have the diffusion blocking effect described above if it contains Ge, As, Se, B, P, Te, Sb, Tl, Pb, or S.
- the concentration of Ge, As, Se, B, P, Te, Sb, Tl, Pb, or S in the electroplated layer 50 is preferably in the range of from 1 ppm to 10000 ppm, inclusive.
- a third embodiment of the present invention provides a method of manufacturing a semiconductor device and also provides a semiconductor device. These method and semiconductor device have many features common to the method and semiconductor device of the first embodiment. Therefore, the following description of the third embodiment will be primarily limited to the differences from the first embodiment.
- FIG. 12 is a cross-sectional view of the semiconductor device of the third embodiment. This semiconductor device has a surface protection layer 58 on its top surface.
- a first adhesion layer 52 is formed on the metal layer 18 .
- the first adhesion layer 52 is formed by immersing the substrate 10 in an electroless NiP plating solution.
- the first adhesion layer 52 is formed of NiP material, which has relatively high internal stress. If a layer of NiP material is formed on a thin substrate to a thickness of 1 ⁇ m or more, the substrate will warp. In order to avoid this problem, the thickness of the first adhesion layer 52 is preferably less than 1 ⁇ m. It should be noted that a Ni film having a thickness of 1 ⁇ m or less tends to have pinholes if it is formed by electroplating, but does not if it is formed by electroless plating.
- a surface diffusion blocking layer 54 is formed on the first adhesion layer 52 by electroplating.
- the substrate 10 is immersed in a Pd plating solution containing Ge oxide, and a DC power supply is connected to the substrate and a separate platinum-coated titanium electrode (which is also immersed in the Pd plating solution) so that the substrate acts as a cathode and the titanium electrode acts as an anode.
- a current is then applied between the cathode (the substrate) and the anode (the titanium electrode) to form the surface diffusion blocking layer 54 .
- a second adhesion layer 56 is then formed on the surface diffusion blocking layer 54 .
- the second adhesion layer 56 is formed in the same manner as the first adhesion layer 52 .
- a surface protection layer 58 is then formed on the second adhesion layer 56 .
- the surface protection layer 58 is formed of Au and produced by immersing the substrate 10 in a displacement Au plating solution.
- the displacement Au plating solution contains, e.g., sodium gold sulfite, a sulfite salt, or a chelating agent.
- the gold concentration in the solution is preferably 1-5 g/L.
- the temperature of the plating bath is preferably approximately 60-80° C.
- the surface protection layer 58 of Au which is an oxidation resistant material, covers and is exposed at the top surface of the semiconductor device of the third embodiment. This prevents oxidation and corrosion of the metal layer 18 , resulting in improved moisture resistance and improved stability in characteristics of the semiconductor device. Further, since the surface protection layer 58 is made of Au, it has increased solder wettability, facilitating wetting of the top surface of the semiconductor device with solder.
- the surface diffusion blocking layer 54 is formed on the Cu metal layer 18 by electroplating, it is unlikely that Cu in the metal layer will diffuse to the surface protection layer 58 via grain boundary diffusion, thus preventing reaction of the metal layer 18 with the surface protection layer 58 and the resulting formation of an alloy.
- the formation of the surface diffusion blocking layer 54 allows for a reduction in the thickness of the surface protection layer 58 , which is formed of expensive Au, resulting in decreased cost of the semiconductor device. It should be noted that die bonding to the surface of the surface protection layer 58 by use of Ag paste or AuSn solder requires heat treatment during or after the bonding process. If it were not for the surface diffusion blocking layer 54 , such heat treatment might result in formation of an alloy of the bonding material and Cu in the metal layer 18 and therefore cause peeling of the bonding material. In the semiconductor device of the third embodiment, however, the presence of the surface diffusion blocking layer 54 prevents such alloy formation.
- the material of the first and second adhesion layers 52 and 56 may be any suitable Ni- or Ti-based metal. Further, the first adhesion layer 52 is not required if the adhesion between the metal layer 18 and the surface diffusion blocking layer 54 is sufficient without the first adhesion layer 52 , and the second adhesion layer 56 is not also required if the adhesion between the surface diffusion blocking layer 54 and the surface protection layer 58 is sufficient without the second adhesion layer 56 .
- the surface protection layer 58 may be formed of any suitable material having greater oxidation resistance than the metal layer 18 .
- the surface protection layer 58 may be formed of a noble metal such as Pt, Pd, or Rh.
- the surface protection layer 58 may be formed of an insulator, such as silicon oxide, silicon nitride, polyimide, or BCB, or a semiconductor, such as silicon.
- the surface diffusion blocking layer 54 is preferably formed by electroplating in order to enhance its diffusion blocking effect. Therefore, the surface diffusion blocking layer 54 may be formed of Ni, Pd, Mo, Rh, or Ru by electroplating. Further, the surface diffusion blocking layer 54 may be formed of a metal which provides a greater diffusion blocking effect than Pd. Examples of such metals include Ti, TiN, Ta, TaN, W, and WN. Further, the surface diffusion blocking layer 54 may be produced by electroless plating and formed of a Co-based metal, such as CoWP, or a Ni-based metal, such as NiP, or formed of Pt, Pd, Rh, or Ru. Such an electrolessly plated layer also has some diffusion blocking effect.
- the diffusion blocking effect of the surface diffusion blocking layer 54 need not be as great as that of the diffusion blocking layer 17 , since the surface diffusion blocking layer 54 only needs to prevent diffusion from the metal layer 18 whereas the diffusion blocking layer 17 needs to prevent counter-diffusion between Cu in the metal layer 18 and components of the substrate 10 . Therefore, the surface diffusion blocking layer 54 may be formed of a metal and produced by electroless plating, vapor deposition, or sputtering, etc., instead of electroplating.
- the surface protection layer 58 may be made of a material having greater oxidation resistance than the metal layer 18 and directly formed on and in contact with the metal layer 18 , thereby omitting the first adhesion layer 52 , the surface diffusion blocking layer 54 , and the second adhesion layer 56 .
- the surface protection layer may be formed of, e.g., Pd.
- a Pd layer has greater oxidation resistance than the metal layer 18 of Cu or Ag and has some Cu diffusion blocking effect.
- the above surface protection layer 58 may be formed on the semiconductor device of the second embodiment.
- a fourth embodiment of the present invention provides a method of manufacturing a semiconductor device having a via structure, wherein the via structure is formed by a method similar to that of the third embodiment.
- FIG. 13 is a cross-sectional view of a substrate having an electrode thereon after the electrode has been formed by the first step of the semiconductor device manufacturing method of the fourth embodiment.
- the method of the fourth embodiment proceeds as follows. First, an electrode 60 is formed on the top surface of a substrate 10 A formed of GaAs. In this step, device structures such as transistors are also formed on the top surface of the substrate 10 A.
- FIG. 14 is a cross-sectional view of the substrate 10 A after the support substrate has been bonded thereto. Specifically, in this step, a support substrate 64 of sapphire or synthetic quartz having a thickness of approximately 1 mm and held by an adhesive material 62 such as wax or tape is bonded to the top surface of the substrate 10 A.
- FIG. 15 is a cross-sectional view of the substrate after the via hole has been formed therein. Specifically, in this step, the substrate 10 is etched from the bottom surface side thereof so as to form a via hole 10 a which penetrates through the substrate 10 and extends from the bottom surface of the substrate 10 to the bottom surface of the electrode 60 .
- FIG. 16 is a cross-sectional view of the substrate after the heat-radiating electrode has been formed thereon.
- the heat-radiating electrode 70 has layers described in connection with the third embodiment. Specifically, the heat-radiating electrode 70 includes the Pd—Ga—As layer 12 (formed as a result of adhesion of a metal catalyst to the substrate), the electrolessly plated layer 14 , the electroplated layer 16 , the metal layer 18 , the first adhesion layer 52 , the Pd layer 54 , the second adhesion layer 56 , and the surface protection layer 58 . These layers of the heat-radiating electrode 70 are formed to extend over the inner wall of the via hole 10 a and the bottom surface of the electrode 60 .
- FIG. 17 is an enlarged view of the portion shown in the dashed line of FIG. 16 .
- FIG. 17 shows the layers of the heat-radiating electrode 70 .
- the heat-radiating electrode 70 has significantly high covering ability, since it includes the diffusion blocking layer 17 , which is formed by plating. This means that the diffusion blocking layer 17 can be formed to cover the entire inner wall of the via hole 20 a.
- heat-radiating electrodes which are electrodes having good heat dissipation characteristics. It should be noted that heat-radiating electrodes formed solely of Au are expensive although they have stable characteristics.
- the heat-radiating electrode 70 of the fourth embodiment includes the Cu metal layer 18 , etc., in addition to the surface protection layer 58 of Au, resulting in decreased manufacturing cost of the semiconductor device.
- first adhesion layer 52 , the Pd layer 54 , the second adhesion layer 56 , and the surface protection layer 58 may be omitted from the heat-radiating electrode 70 .
- a fifth embodiment of the present invention provides a method of manufacturing a semiconductor device and also provides a semiconductor device. These method and semiconductor device have many features common to the method and semiconductor device of the first embodiment. Therefore, the following description of the fifth embodiment will be primarily limited to the differences from the first embodiment.
- FIG. 18 is a cross-sectional view of the semiconductor device of the fifth embodiment.
- the electroplated layer 16 is formed of Ru.
- a plated Au layer 100 is provided between the electrolessly plated layer 14 and the electroplated layer 16 . It should be noted that the plated Au layer 100 may be replaced by an Au layer formed by a method other than plating.
- the plated Au layer 100 is formed on the electrolessly plated layer 14 after forming the electrolessly plated layer 14 .
- the substrate is then immersed in an electroplating solution, and the electroplated layer 16 is formed on the plated Au layer 100 using the electrolessly plated layer 14 and the plated Au layer 100 as power feeding layers.
- FIG. 9 is a graph comparing the Cu diffusion blocking effect of two different samples.
- Sample 4 was produced as follows: a first NiP layer (having a thickness of 0.5 ⁇ m) was formed on a GaAs substrate in an electroless plating solution after applying catalyst treatment to the surface of the substrate using a Pd activating solution; a first Pd layer (0.2 ⁇ m) was then formed on the first NiP layer in an electroplating solution containing Ge; a Cu layer (a metal layer having a thickness of 3 ⁇ m) was then formed on the first Pd layer in an electroplating solution; a second NiP layer (0.5 ⁇ m) was then formed on the Cu layer in an electroless plating solution; a second Pd layer (0.2 ⁇ m) was then formed on the second NiP layer in an electroplating solution; and an Au layer (0.05 ⁇ m) was then formed on the second Pd layer in a displacement plating solution.
- the electroplated layer of Sample 4 (between the
- Sample 5 was produced as follows: a first NiP layer (0.5 ⁇ m) was formed on a GaAs substrate in an electroless plating solution after applying catalyst treatment to the surface of the substrate using a Pd activating solution; a first Au layer (0.05 ⁇ m) was then formed on the first NiP layer in a displacement Au plating solution; an Ru layer (0.2 ⁇ m) was then formed on the first Au layer in an electroplating solution; a Cu layer (a metal layer having a thickness of 3 ⁇ m) was then formed on the Ru layer in an electroplating solution; a second NiP layer (0.5 ⁇ m) was then formed on the Cu layer in an electroless plating solution; a Pd layer (0.2 ⁇ m) was then formed on the second NiP layer in an electroplating solution; and a second Au layer (0.05 ⁇ m) was then formed on the Pd layer in a displacement plating solution.
- the electroplated layer of Sample 5 (between the GaAs substrate and the Cu layer) is a Ru layer. It should be noted that a sample similar to Sample 5 but without the first plated Au layer was found to have cracks in a portion of the electroplated Ru layer, whereas the electroplated Ru layer of Sample 5 was found to have substantially no cracks since Sample 5 has the first plated Au layer.
- the reason that the Ru layer has a greater Cu diffusion blocking effect is that the melting point (2050° C.) of Ru is higher than the melting point (1552° C.) of Pd and hence the Ru layer has higher thermal stability than the Pd layer. It should be noted that features of the semiconductor manufacturing methods and the semiconductor devices of embodiments described above may be combined where appropriate.
- a diffusion blocking layer that includes two layers formed by electroless plating and electroplating, respectively, is provided between a substrate and a metal layer of, e.g., Cu.
- the diffusion blocking layer has high covering ability, since the entire diffusion blocking layer is formed by plating.
- the electroplated layer of the diffusion blocking layer serves to reduce diffusion of components of the metal layer, such as Cu, into the substrate.
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CN103789764B (zh) | 2016-06-08 |
KR101542765B1 (ko) | 2015-08-07 |
JP2014112634A (ja) | 2014-06-19 |
TWI492280B (zh) | 2015-07-11 |
CN103789764A (zh) | 2014-05-14 |
KR20140055961A (ko) | 2014-05-09 |
US20140117549A1 (en) | 2014-05-01 |
TW201426832A (zh) | 2014-07-01 |
JP5725073B2 (ja) | 2015-05-27 |
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